Manufacture of azo-dyestuffs containing sulphur from diazotized orthoaminophenols



Patented S ept. 1 1 1934 UNITED STATES PATENT OFFICE MANUFACTURE OF AZO-DYESTUFFS CON- TAINING .SULPHUR FROM DIAZOTIZED ORTHOAMINOPHENOLS Robert Lantz, Paris, France, assignor of one-half to Societe Anonyme des Matieres Colorantes &

Produits Ghimiques France de Saint-Denis, Paris,

No Drawing. Application June 11, 1931, Serial No. 543,747. In France June 20,1930,

17 Claims.

This invention relates to the manufacture of dyestufis by coupling a diazotized orthoaminophenol which may or may not contain substitu-,

nols, such as chloro-orthoamino, picramic acid whose structural formula is:-

N02 NH:

7 N02 or the like.

Example 2.--22 parts of ortho-aminophenol whose structural formula is:

The following examples illustrate the invention the parts being by weight:

Example 1.--7.2 parts of 4-nitro-2-amino-1- phenol whose structural formula is:

NO: are dissolved in 18 parts of commercial hydrochloric acid and 200 parts of water and there are added 3.5 parts of a solution of sodium nitrite of 10 per cent. strength so that there is present an excess of nitrous acid. The diazo solution thus prepared is introduced into asolution containing 15 parts of the dithioanilide of ,B-hydroxynaphthoic acid, (which may be made in the manner described in Example 3 of my U. S. patent application No. 543,746; and Whose structural formula is:

7 are dissolved in 70 parts of hydrochloric acid of 22 B. and 600 parts of waterand diazotized at about 0 C. by the addition of 150 parts of a solutionof sodium nitrite of 10 per cent strength. The diazo solution thus prepared is introduced into a solution of 35 parts of bis (2 hydroxynaphthyl 6). disulphide whose structural formula is HO -03 (Zincke et Dereser Ber. 51, 1918, page 357) in 280 parts of caustic soda solution of 40 Be. and 1200 parts of water. Coupling occurs slowly yielding a dark violet-blue dyestufi the whole is allowed to stand overnight and the dyestuff is then separated by filtration;

dissolved in 35 parts of caustic soda solution of 40 B., 150 parts of water and 120 parts of alcohol. The dyestufl separates in the form of a black precipitate which is filtered and washed with water.

The para-para-dithioanilide of p hydroxy-r naphthoic acid maybe coupled in an analogous manner with various diazotized orthoaminophe- Example 3.-16 parts of 4-chloro-2-amino-1- phenol whose structural formula is:

are dissolved in 36 parts of hydrochloric acid and 200 parts of water and diazotized by the addition of parts of a solution of sodium nitrite of 10 per cent strength. The diazo solution is introduced into 20 parts of trisulphide of u-naphtholi whose formula is (C10H7OH)2S3 and whose structural formula is not known; (Watson and Dutt, Journ. Chem. Soc. 121p. 24184)) dissolved in 70 parts of caustic soda solution of 44 Be. and 400 parts of water. Precipitation of the dyestuif occurs rapidly; it is separated by filtration.

The properties of a number of dyestuffs obtain' able in accordance with the invention are indiwhich comprises coupling a diazotized aromatic amine having a hydroxy-group in the ortho position with respect to the amino group with an azo-component the molecule of which comprises a group --SS--S-.

10. A method of manufacturing azo-dyestuifs which comprises coupling diazotized chloroortho-aminophenol with trisulphide of dl 1a/p11- thol. r

115A method of manufacturing azo-dyestuifs which comprises coupling a diazotized aromatic amine having an hydroxy-group in the ortho position with respect to the amino group with trisulphide of rnaphthol;

Gated i the owi table: 12. Azodyestuffs formed by coupling a diazo Diazo compound of A20 component Color of the dyestufi gg i ffl l s ll f il l e Color of Solution in V 1 powder 1 solution p sulphuric acid Ohloro-ortho-aminopbenol Para-para-di-thi oanilide of B-hy- B1uish-black Blue.

(lroxynaphthoic acid. Nitro-orthoaminophenol -.do Greenish-black Violet. Picramic acid B k Vivid red-purple. Ortho-amino-phenol B1s 2 hydroxy-naphthyl 1su1- Red-purple.

p 1 e. Chloro-ortho-aminophenol Trisulphideofa-naphtho Reddish-black Purple-grey.

What I claim is:

1. A method of manufacturing azo-dyestuifs which comprises diazotizing 4-chloro-2-arninol-phenol, introducing the diazo solution thus prepared. into a solution of trisulphide of a-naphthol in caustic soda and water and separating by filtration the precipitated dyestuif.

2. A method of manufacturing azo-dyestuffs which comprises coupling a diazotized aromatic amine having an hydroXy-group in the ortho position with respect to the amino-group with an a o-component the molecule of which contains at least one group Sn, n being an integer greater than 1 and smaller than 4'.

3. A method of manufacturing azo-dyestuifs which comprises coupling a diazotized aromatic amine having an hydroXy-group in the ortho po-' sition with respect-to the amino group with an azo component-the molecule of which comprises one group Sn, n being an integer greater than 1 and sma er'than j 4. A method of manufacturing azo-dyestufis which comprises coupling a diazotized aromatic amine having a hydroxy-group in' the ortho position with respect to the amino group with an azo component the molecule of which comprises a group S--S.

5. A method of manufacturing azo-dyestuffs which comprises coupling a diazotized aromatic amine having a hydroxy-group in the'ortho po sition will respect to the aminogroup with para paradithioanilide of o-hydroxynaphthoic acid.

6. A method of manufacturing azodyestuifs which comprises coupling diaaotized nitro orthoaminophenol with para-para-dlthioanilide of ,8- w v ofdiazotized ortho-aminophenol and bi (2 layhydroxynaphthoic acid.

'7. A method of manufacturing azo-dyestufls Which-comprises coupling a diazotized aromatic amine having a hydroxy-group in the ortho position with respect to the amino group with his (2 hydroxynaphthyl 6) disulphide.

8. A method of manufacturing azo-dyestuffs which comprises coupling diazotized ortho -a1ninophenol with his (2 hydroxynaphthyl 6) disulphide.

9. A method of manufacturing azo-dyestuffs tized aromatic amine having a hydroXy-group in the ortho position with respect to the aminogroup with an azo-component the molecule of which contains at least one group a being integer greater than 1 and smaller than 4s, these azodyestuifs being capable of being absorbed by cotton and giving very fast dyeings when treated by metal salts. p i

13. Azodyestuifs formed by coupling a diazotized aromatic amine having a hydroXy-group inithe ortho position with respect to the aminogroup with an azo-component the molecule of which contains at least one group Sn, n being an integer greater than 1 and smaller than 4, these azodye'stuifs being soluble in sodium sulphide and sulphuric acid, being. capable of being-absorbed by cotton and similar materials and giving very fast dyeings when treated by metal salts.

l4. Azodyestuifs formedby coupling a diazotized aromatic amine having a hydroxy-group in the ortho position with respect to the amino group with an azo-component the molecule of which contains at least one group Sn, 1t being an integergreater than 1 and small r than 4, these 1 'droxynaphthyl/d)-disulphide forming a bluish black powder giving a blue solution in sodium sulphide, and a red-purple solution in sulphuric acid.

sulphide of 'u-naphthol forming a reddish-black powder giving a red solution in sodium sulphide and a-purple'grey solution in sulphuric acid.

' ROBERT LANTZ,

17. As a new compound, the coupling product of dia zotizod chloro-ortho aminophenol and tri- 

